EP3156127B1 - Composition catalytique contenant un ligand à base de phosphore, et procédé d'hydroformylation l'utilisant - Google Patents

Composition catalytique contenant un ligand à base de phosphore, et procédé d'hydroformylation l'utilisant Download PDF

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EP3156127B1
EP3156127B1 EP15871290.1A EP15871290A EP3156127B1 EP 3156127 B1 EP3156127 B1 EP 3156127B1 EP 15871290 A EP15871290 A EP 15871290A EP 3156127 B1 EP3156127 B1 EP 3156127B1
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group
monodentate
ligand
phosphite
catalyst composition
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EP3156127A1 (fr
EP3156127A4 (fr
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Mi Young Kim
Min Ji Choi
Sung Shik Eom
Dong Hyun Ko
Da Won Jung
Tae Yun Kim
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LG Chem Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2495—Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Definitions

  • the present invention relates to a catalyst composition containing a phosphorous-based ligand and a hydroformylation process using the same. More specifically, the present invention relates to a catalyst composition which reduces an N/I ratio (ratio of normal to iso) of aldehyde produced by hydroformylation of an olefin-based compound and exhibits superior catalytic activity and stability, and a hydroformylation process of an olefin-based compound using the same.
  • N/I ratio ratio of normal to iso
  • a hydroformylation reaction wherein linear (normal) and branched (iso) aldehydes, in which the number of carbon atoms is increased by one, are prepared by reacting various olefins with carbon monoxide (CO) and hydrogen (H 2 ), commonly called “synthetic gas", in the presence of a homogeneous organometallic catalyst and a ligand was first found by Otto Roelen in 1938 in Germany.
  • CO carbon monoxide
  • H 2 hydrogen
  • the hydroformylation reaction known as an oxo reaction is an industrially important reaction in the homogeneous catalyst reaction and various aldehydes including alcohol derivatives are produced and used all over the world through the oxo process.
  • oxo alcohol Various aldehydes synthesized through the oxo reaction may undergo condensation reaction of aldol or the like and may then be converted into various acids and alcohols containing a long alkyl group through oxidization or hydrogenation.
  • the hydrogenated alcohol obtained by this oxo reaction is referred to as an oxo alcohol.
  • the oxo alcohol is widely industrially used for solvents, additives, materials for various plasticizers, synthetic lubricants and the like.
  • Patent Document 1 KR 2001-0052204 A
  • EP 2 881 173 A1 discloses a catalyst composition and a method of hydroformylating olefin using the same, which catalyst composition comprises a triphenylphosphine-based compound having a substituent group at a para-position, a diphenylphosphine-based compound, and a transition metal catalyst.
  • the present invention has been made in view of the above problems, and it is one object of the present invention to provide a catalyst composition which reduces an N/I (normal/iso) ratio (selectivity) of aldehyde produced by hydroformylation of an olefin-based compound and exhibits superior catalytic activity and stability.
  • a catalyst composition including a monodentate phosphite ligand represented by the following Formula 1, a monodentate phosphine ligand represented by the following Formula 2, and a transition metal catalyst represented by the following Formula 3, wherein the total content of the entire ligand including the monodentate phosphite ligand and the monodentate phosphine ligand is 1 to 33 moles, based on 1 mole of the transition metal catalyst, wherein R 1 , R 2 , R 3 , R' 1 , R' 2 and R' 3 each independently represent: a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms group; or a substituted or unsubstituted aryl group having 6 to 36 carbon atoms; and when R 1 , R 2 , R 3 , R' 1 , R' 2 and R' 3 are substituted by
  • M is one selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os)
  • L 1 , L 2 and L 3 each independently represent one selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) and acetylacetonato (AcAc)
  • x, y and z each independently represent 0 to 5, with the proviso that all of x, y and z are not zero, wherein the content of each of the monodentate phosphite ligand and the monodentate phosphine ligand is 0.5 to 32.5 moles, based
  • a hydroformylation method of an olefin-based compound including reacting an olefin-based compound with a synthetic gas (CO/H 2 ) of carbon monoxide and hydrogen in the presence of the catalyst composition, to prepare aldehyde.
  • a synthetic gas CO/H 2
  • the present invention has an effect of providing a catalyst composition which reduces an N/I (normal/iso) ratio of aldehydes produced by hydroformylation of an olefin-based compound and exhibits superior catalytic activity and stability.
  • the present invention has an effect of providing a hydroformylation method of an olefin-based compound using the catalyst composition.
  • the present inventors found that, when both a monodentate phosphite ligand and a monodentate phosphine ligand are applied to a catalyst composition used for hydroformylation of olefin, N/I (ratio of normal to iso) selectivity is reduced, and catalytic activity and stability are improved, as compared to a conventional catalyst composition to which either a phosphite ligand or a phosphine ligand is applied.
  • N/I ratio of normal to iso
  • the catalyst composition according to the present invention contains: a monodentate phosphite ligand; a monodentate phosphine ligand; and a transition metal catalyst.
  • the monodentate phosphite ligand is a compound represented by the following Formula 1. wherein R 1 , R 2 and R 3 are each independently a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 36 carbon atoms; and when R 1 , R 2 and R 3 are substituted by a substituent, the substituent is for example nitro (-NO 2 ), fluorine (-F), chlorine (-Cl), bromine (-Br) or an alkyl group having 1 to 20 carbon atoms.
  • examples of the monodentate phosphite ligand include one or more selected from the group consisting of triphenyl phosphite, tris(2,6-di-tert-butyl-4-methoxyphenyl)phosphite, tris(2-tert-butyl-4-methylphenyl)phosphite and tris(2,4-di-tert-butylphenyl)phosphite (TDTBPP).
  • TDTBPP tris(2,4-di-tert-butylphenyl)phosphite
  • the monodentate phosphine ligand is a compound represented by the following Formula 2. wherein R' 1 , R' 2 and R' 3 are each independently a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms; a substituted or unsubstituted aryl group having 6 to 36 carbon atoms; or a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms; and when R' 1 , R' 2 and R' 3 are substituted by a substituent, the substituent is for example nitro (-NO 2 ), fluorine (-F), chlorine (-Cl), bromine (-Br) or an alkyl group having 1 to 20 carbon atoms.
  • R' 1 , R' 2 and R' 3 are each independently a substituted or unsubstituted cycloalkyl or cycloalkenyl group having 5 to 20 carbon atoms; a substituted or un
  • examples of the monodentate phosphine ligand include one or more selected from the group consisting of tri-m-tolylphosphine (TMTP), tri-p-tolylphosphine (TPTP), diphenyl(p-tolyl)phosphine (DPPTP), cyclohexyldiphenylphosphine (CHDP), tris(2,6-dimethoxyphenyl)phosphine (TDMPP), tris(4-methoxyphenyl)phosphine (TMPP), trimesitylphosphine (TMSTP), tris-3,5-xylylphosphine (TXP), tricyclohexylphosphine (TCHP), tribenzylphosphine (TBP), and benzyl diphenylphosphine (BDPP).
  • TMTP tri-m-tolylphosphine
  • TPTP tri-p-tolylphosphine
  • DPPTP dipheny
  • the monodentate phosphite ligand and the monodentate phosphine ligand may each be present in an amount of 0.5 to 32.5 moles, 1 to 30 moles, 1 to 25 moles, or 5 to 20 moles, based on 1 mole of the transition metal catalyst. In this case, there are effects of superior catalytic activity and reaction rate.
  • the entire ligand including the monodentate phosphite ligand and the monodentate phosphine ligand may, for example, be present in an amount of 1 to 33 moles, 1 to 30 moles, 1 to 29 moles, 10 to 29 moles, or 15 to 29 moles, based on 1 mole of the transition metal catalyst. In this case, there is an effect of superior catalyst stability.
  • a mix ratio between the monodentate phosphite ligand and the monodentate phosphine ligand is 5:1 to 1:5, 3:1 to 1:3, or 2:1 to 1:2, based on weight.
  • N/I ratio ratio of normal to iso
  • the transition metal catalyst is a catalyst represented by the following Formula 3.
  • Formula 3 M(L 1 ) x (L 2 ) y (L 3 ) z wherein M may, for example, be selected from the group consisting of cobalt (Co), rhodium (Rh), iridium (Ir), ruthenium (Ru), iron (Fe), nickel (Ni), palladium (Pd), platinum (Pt) and osmium (Os),
  • L 1 , L 2 and L 3 may, for example, be each independently selected from the group consisting of hydrogen, carbonyl (CO), cyclooctadiene, norbornene, chlorine, triphenylphosphine (TPP) and acetylacetonato (AcAc)
  • x, y and z may, for example, be each independently 0 to 5, with the proviso that all of x, y and z are not zero.
  • examples of the transition metal catalyst include one or more selected from the group consisting of cobalt carbonyl [Co 2 (CO) 8 ], acetylacetonato dicarbonyl rhodium [Rh(AcAc) (CO) 2 ], acetylacetonato carbonyl triphenylphosphine rhodium [Rh(AcAc)(CO)(TPP)], hydridocarbonyltri(triphenylphosphine) rhodium [HRh(CO) (TPP) 3 ], acetylacetonatodicarbonyl iridium [Ir(AcAc)(CO) 2 ) and hydridocarbonyltri(triphenylphosphine) iridium [HIr(CO)(TPP) 3 ]. In this case, there is an effect of superior catalytic activity.
  • the transition metal catalyst may, for example, be present in an amount of 1 to 1,000 ppm, 10 to 800 ppm, or 50 to 500 ppm, based on the catalyst composition. Within this range, there is an effect of superior hydroformylation rate.
  • the catalyst composition may, for example, contain further one or more solvents selected from the group consisting of propane aldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, ethanol, pentanol, octanol, hexanol, benzene, toluene, xylene, orthodichlorobenzene, tetrahydrofuran, dimethoxyethane, dioxane, methylene chloride and heptane.
  • solvents selected from the group consisting of propane aldehyde, butyl aldehyde, pentyl aldehyde, valeraldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, aceto
  • the hydroformylation method according to the present invention includes reacting an olefin-based compound with a synthetic gas (CO/H 2 ) of carbon monoxide and hydrogen in the presence of the catalyst composition to prepare aldehyde.
  • a synthetic gas CO/H 2
  • the olefin-based compound may, for example, be a compound represented by the following Formula 4.
  • R 4 and R 5 are, for example, each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, fluorine (F), chlorine (Cl), bromine (Br), trifluoromethyl (-CF 3 ) or an aryl group having 6 to 20 carbon atoms and having 0 to 5 substituents, wherein the substituent of the aryl group is for example nitro (-NO 2 ), fluorine (-F), chlorine (-Cl), bromine (-Br), methyl, ethyl, propyl or butyl.
  • the olefin-based compound may include one or more selected from the group consisting of ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene and styrene.
  • a mix ratio of carbon monoxide to hydrogen of the synthetic gas may be 5:95 to 70:30, 40:60 to 60:40, or 45:55 to 55:45, on a mole basis. Within this range, there is an effect in that catalyst reactivity is superior because the gas used for reaction does not accumulate in the reactor.
  • hydroformylation method of the olefin-based compound according to the present invention so long as a catalyst composition is used for the hydroformylation method.
  • a temperature at which the olefin-based compound reacts with the synthetic gas (CO/H 2 ) in the presence of a catalyst composition may be 20 to 180°C, 50 to 150°C, or 75 to 125°C. In this case, there is an effect of maintaining catalyst stability and activity during hydroformylation.
  • a reaction pressure in the reactor may be 1 to 700 bar, 1 to 300 bar, or 5 to 30 bar. Within this range, there is an effect of superior catalytic activity.
  • the hydroformylation method of the olefin-based compound may, for example, be represented by the following Reaction Scheme 1.
  • aldehyde can be prepared by dissolving the transition metal catalyst represented by Formula 3, and the monodentate phosphite ligand and the monodentate phosphine ligand represented by Formulae 1 and 2 in the solvent to prepare a mixed solution of a transition metal catalyst and a ligand, charging the mixed solution, the olefin-based compound represented by Formula 4 and the synthetic gas (CO/H 2 ) in an ordinary reactor and performing hydroformylation at an elevated temperature and a predetermined pressure while stirring.
  • the normal/iso ratio of aldehyde prepared by hydroformylation method of the olefin-based compound may, for example, be 1.5 to 3.0, 1.8 to 2.95, or 1.95 to 2.95.
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphite compound (L1) and a phosphine compound (L2) were added as ligands in moles as set forth in Table 1, instead of triphenylphosphine (TPP).
  • TPP triphenylphosphine
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphite compound (L1) was added in a mole as set forth in Table 1 as a ligand, instead of triphenylphosphine (TPP).
  • a phosphite compound (L1) was added in a mole as set forth in Table 1 as a ligand, instead of triphenylphosphine (TPP).
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphine compound (L2) was added in a mole as set forth in Table 1 as a ligand, instead of triphenylphosphine (TPP).
  • L2 phosphine compound
  • TPP triphenylphosphine
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphite compound (L1) and a phosphine compound (L2) were added in moles as set forth in Table 1 as ligands, instead of triphenylphosphine (TPP).
  • a phosphite compound (L1) and a phosphine compound (L2) were added in moles as set forth in Table 1 as ligands, instead of triphenylphosphine (TPP).
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a bidentate phosphite compound (L3) and a phosphine compound (L2) were added in moles as set forth in Table 2 as ligands, instead of triphenylphosphine (TPP).
  • L3 bidentate phosphite compound
  • L2 phosphine compound
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphite compound (L1) and a phosphite compound (L1') were added in moles as set forth in Table 3 as ligands, instead of triphenylphosphine (TPP).
  • TPP triphenylphosphine
  • Catalyst compositions were prepared in the same manner as in Reference Example except that a phosphine compound (L2) and a phosphine compound (L2') were added as set forth in Table 4 as ligands, instead of triphenylphosphine (TPP).
  • a phosphine compound (L2) and a phosphine compound (L2') were added as set forth in Table 4 as ligands, instead of triphenylphosphine (TPP).
  • Catalytic activity (normal activity, %): the total amount of normal and isobutyl aldehydes produced by reaction in accordance with each of Examples and Comparative Examples, was compared with respect to the total amount of normal and isobutyl aldehydes produced by reaction in accordance with Comparative Example, based on 100%, and catalytic activity was calculated and expressed as a percentage in accordance with the following Equation 1.
  • Catalytic activity the total amount of normal and isobutyl aldehydes of Example or Comparative Example / the total amount of normal and isobutyl aldehydes of Reference Example ⁇ 100
  • Catalyst stability (normal stability, %): obtained by performing reaction in accordance with Reference Example, measuring the amount of propylene gas used for reaction, inactivating catalyst solutions prepared in Examples and Comparative Examples for 24 hours, conducting hydroformylation in the same manner as above, measuring the amount of propylene gas used for reaction, comparing the amount of consumed propylene gas before inactivation of Reference Example with the amount of consumed propylene gas after inactivation of Example or Comparative Example for 24 hours, calculating catalyst stability in accordance with the following Equation 2 and expressing the same as a percentage.
  • Catalyst stability amount of propylene gas consumed during reaction after inactivation of Example or Comparative Example for 24 hours / amount of consumed propylene gas before inactivation of Reference Example ⁇ 100
  • catalyst compositions of Examples 1 to 4 prepared according to the present invention maintained similar or superior catalytic activity and stability, and significantly reduced normal/iso selectivity (n/i ratio) of produced aldehyde, as compared to Reference Example.
  • Comparative Examples 1 to 4 in which only a phosphite compound was used as a ligand exhibited significant deterioration in catalyst stability and Comparative Examples 5 to 10 in which only a phosphine compound was used as a ligand exhibited deteriorated catalytic activity or did not exhibit a level of selectivity desired in the present invention.

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Claims (10)

  1. Composition catalytique comprenant :
    un ligand de phosphite monodenté représenté par la formule 1 suivante ;
    un ligand de phosphine monodenté représenté par la formule 2 suivante ; et
    un catalyseur de métal de transition représenté par la formule 3 suivante,
    dans laquelle la teneur totale de la totalité du ligand, y compris du ligand de phosphite monodenté et du ligand de phosphine monodenté est de 1 à 33 moles, par rapport à 1 mole du catalyseur de métal de transition,
    Figure imgb0015
    Figure imgb0016
    dans lesquelles R1, R2, R3, R'1, R'2 et R'3 représentent chacun indépendamment : un cycloalkyle substitué ou non substitué ou un groupe cycloalkyle portant 5 à 20 atomes de carbone ; ou un groupe aryle substitué ou non substitué portant 6 à 36 atomes de carbone ; et
    lorsque R1, R2, R3, R'1, R'2 et R'3 sont substitués par un substituant, le substituant est le nitro (-NO2), le fluor (-F), le chlore (-Cl), le brome (-Br) ou un groupe alkyle portant 1 à 20 atomes de carbone,


            [Formule 3]     M(L1)x(L2)y(L3)z

    dans laquelle M est un composé sélectionné dans le groupe constitué de cobalt (Co), de rhodium (Rh), d'iridium (Ir), de ruthénium (Ru), de fer (Fe), de nickel (Ni), de palladium (Pd), de platine (Pt) et d'osmium (Os),
    L1, L2 et L3 représentent chacun indépendamment un composé sélectionné dans le groupe constitué d'hydrogène, de carbonyle (CO), de cyclooctadiène, de norbornène, de chlore, de triphénylphosphine (TPP) et d'acétylacétonate (AcAc), et
    x, y et z représentent chacun indépendamment 0 à 5, à la condition que tous les x, y et z ne valent pas 0, dans laquelle la teneur de chacun du ligand de phosphite monodenté et du ligand de phosphine monodenté est de 0,5 à 32,5 moles, par rapport à 1 mole du catalyseur de métal de transition, un rapport de mélange du ligand de phosphite monodenté et du ligand de phosphine monodenté étant de 5:1 à 1:5, par rapport au poids.
  2. Composition catalytique selon la revendication 1, dans laquelle le ligand de phosphite monodenté comprend un ou plusieurs composants sélectionnés dans le groupe constitué de phosphite de triphényle, de tris (2,6-di-tert-butyl-4-méthoxyphényl) phosphite, de tris (2-tert-butyl-4-méthylphényl) phosphite et de tris (2,4-di-tert-butylphényl) phosphite (TDTBPP).
  3. Composition catalytique selon la revendication 1, dans laquelle le ligand de phosphine monodenté comprend un ou plusieurs composés sélectionnés dans le groupe constitué de tri-m-tolylphosphine (TMTP), de tri-p-tolylphosphine (TPTP), de diphényl (p-tolyl) phosphine (DPPTP), de cyclohexyldiphénylphosphine (CHDP), de tris (2,6-diméthoxyphényl) phosphine (TDMPP), de tris (4-methoxyphényl) phosphine (TMPP), de trimésitylphosphine (TMSTP), de tris-3,5-xylylphosphine (TXP), de tricyclohexylphosphine (TCHP), de tribenzylphosphine (TBP), et de diphénylphosphine de benzyle (BDPP).
  4. Composition catalytique selon la revendication 1, dans laquelle le catalyseur de métal de transition comprend un ou plusieurs composés sélectionnés dans le groupe constitué de carbonyl-cobalt [Co2(CO)8], d'acétylacétonatodicarbonyle-rhodium [Rh(AcAc)(CO)2], d'acétylacétonatodicarbonyletriphénylphosphine-rhodium [Rh (AcAc) (CO) (TPP)], d'hydridocarbonyltri (triphénylphosphine) rhodium [HRh(CO)(TPP) 3], d'acétylacétonatodicarbonyle-iridium [Ir(AcAc)(CO)2] et d'hydridocarbonyltri (triphénylphosphine) iridium [HIr(CO)(TPP)3].
  5. Composition catalytique selon la revendication 1, comprenant en outre un ou plusieurs solvants sélectionnés dans le groupe constitué de propane aldéhyde, de butyl aldéhyde, de pentyl aldéhyde, de valeraldéhyde, d'acétone, de méthyl-éthyl-cétone, de méthyl-isobutyl-cétone, d'acétophénone, de cyclohexanone, d'éthanol, de pentanol, d'octanol, d'hexanol, de benzène, de toluène, de xylène, d'orthodichlorobenzène, de tétrahydrofurane, de diméthoxyéthane, de dioxane, de chlorure de méthylène et d'heptane.
  6. Composition catalytique selon la revendication 1, dans laquelle la teneur en catalyseur de métal de transition est de 1.000 ppm, par rapport à celle de la composition catalytique.
  7. Procédé d'hydroformylation d'un composé à base d'oléfine comprenant la mise en réaction d'un composé à base d'oléfine avec un gaz synthétique (CO/H2) de monoxyde de carbone et d'hydrogène en présence de la composition catalytique selon l'une quelconque des revendications 1 à 6, de manière à préparer de l'aldéhyde.
  8. Procédé d'hydroformylation selon la revendication 7, dans lequel le composé à base d'oléfine est un composé représenté par la formule 4 suivante :
    Figure imgb0017
    dans laquelle R4 et R5 représentent chacun indépendamment l'hydrogène, un groupe alkyle portant 1 à 20 atomes de carbone, le fluor (F), le chlore (Cl), le brome (Br), le trifluorométhyle) (-CF3) ou un groupe aryle portant 6 à 20 atomes de carbone et ayant 0 à 5 substituants,
    dans laquelle le substituant du groupe aryle est le nitro (-NO2), le fluor (-F), le chlore (-Cl), le brome (-Br), le méthyle, l'éthyle, le propyle ou le butyle.
  9. Procédé d'hydroformylation selon la revendication 7, dans lequel le composé à base d'oléfine comprend un ou plusieurs composés sélectionnés dans le groupe constitué d'éthène, de propène, de 1-butène, de 1-pentène, de 1-hexène, de 1-octène et de styrène.
  10. Procédé d'hydroformylation selon la revendication 7, dans lequel le rapport de mélange de monoxyde de carbone et de l'hydrogène dans le gaz synthétique (CO/H2) est de 5 : 95 à 70 : 30, sur une base molaire.
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